Process for dyeing cellulose textile materials with quaternized reactive dyestuffs



United States Patent 3,416,875 PROCESS FOR DYEING CELLULOSE TEXTILE MATERIALS WITH QUATERNIZED REACTIVE DYESTUFFS Sandro Ponzini, Saronno, Paolo Castelli, Cesano Maderno, and Jean S. Lawendel, Milan, Italy, assignors to idziende Colori Nazionali Aflini ACNA S.p.A., Milan,

taly N0 Drawing. Filed July 16, 1965, Ser. No. 472,668 Claims priority, application Italy, July 17, 1964, 15,658/ 64 9 Claims. c1. s 54.2

QUATERNIZED REACTIVE DYESTUFFS This invention relates to a series of reactive triazine dyestuffs capable of being absorbed and chemically fixed on cellulose fibers by either a cold or warm dyeing process.

The dyestulfs of the present invention are prepared by a quaternization reaction of the reactive triazine dyestuffs having the general formula:

wherein X is selected from the group consisting of H, CH OCH and OC H n is an integer from 1 to 4, and chromogen means the colored residue of a dyestulf selected from the group consisting of azo-dyestulfs, metallized-azo-dyestutfs, anthraquinone dyestuffs and phthalocyanine dyestuffs.

The reactive quaternized dyestuffs of the present invention have the general formula:

Chromogen-NH-C wherein X and n have the above mentioned meanings and m is 1 or 2. The chromogen may be an azoic, azoicmetallized anthraquinone or phthalocyanine dyestuff.

According to the preferred embodiment of the present invention, the reactive quaternized dyestuffs are prepared by reacting a metal salt of isonicotinic acid with the reactive dyestulfs of the general Formula I.

In this manner, reactive dyestuffs are obtained which have improved characteristics for application in dyeing, with dyeing yields increased remarkably and showing the advantage of possible cold or Warm application.

It is unexpected that the quaternization of the dyestuffs of the general Formula I with a metal salt of isonicotinic acid generally permits obtaining, by the cold method, dyeing yields higher than those obtainable by the use of a dyeing catalyst based on other organic tertiary amines, and particularly with respect to the aliphatic tertiary amines, such as asymmetric dimethylhydrazine. This is especially surprising because it is known that the hydro-solubilizing substituents (SO H, COOH) diminish the afiinity of dyestuffs for cellulose fibers.

Also in the dyeing by the warm process (60-90 C.) of cellulose materials with the same quaternized reactive dyestuffs, improvements in dyeing yields are noticed with respect to the starting dyestuffs. Thus the class of reactive dyestuffs of the present invention can be advantageously applied both at warm and cold temperatures.

The use of isonicotinic acid as the quaternizing agent of the above mentioned chlorotriazine dyestuffs generally produces the following advantages with respect to the use of other quaternizable tertiary amines, namely:

(1) Dyeing of cellulose fibers by the cold process without adding dyeing catalysts.

(2) Increasing remarkably, in most cases the dyeing yields, particularly in the cold dyeing process, even when compared to the use of known dyeing catalysts based on aliphatic tertiary amines.

(3) In contrast to the other tertiary amines, isonicotinic acid is odorless, and therefore the dye baths both cold and warm, are completely free of disagreeable or irritating odors.

(4) Increasing of the dye solubility in the cases where it is particularly poor.

(5) Possibility of dyeing cellulose materials in a warm dye bath by generally used processes, using the same quaternized dyes in those particular cases where practical considerations might suggest this method as the preferable one.

The use of isonicotinic acid, also from the point of view of the costs, is advantageous because the excess of isonicotinic acid used in the quaternization reaction may be easily recovered from the mother liquors by filtration, after acidification of these mother liquors, and then it may be reused.

The quaternization is generally carried out by dissolving the reactive dyestuff to be used in a 2% solution of a metal salt of the isonicotinic acid.

The reaction temperature may be varied within wide wide limits, but it is preferably kept between 60 and C. The reaction rate is obviously influenced by the selected temperature and may be controlled by chromatographic analysis.

While the present invention is described with respect to specific examples, it is to be understood that these examples are for purposes of illustration only and that the invention is not limited thereto, since many variations and modifications can be practiced, without departing from its spirit and scope.

The parts and the percentages, unless differently specified, are intended as parts and percentages by weight.

EXAMPLE 1 2 parts of isonicotinic acid are dissolved in parts of water at 70 C. together with 0.64 part of 100% NaOH.

5 parts of the dyestuff ofiHioornTr (I)H SOsNa $1 Q0 T l l NaO s so Na NH- 1 a 3 N IQ (EH2 SOaNB.

are added to the solution.

The solution is kept at this temperature for a whole night (about 15 hours); the dyestutf after salting with NaCl is separated by filtration and dried at 60 C. It may be also separated by direct drying.

The dyestuff obtained dyes cotton at a temperature of 3540 C. with very good tinctorial yields, in a red shade having very good fastness to washing.

The dyestuff to be quaternized used in the process of this example can be obtained as follows:

0.1 mol (18.44 g.) of cyanuric chloride is dissolved 0 in l00150 parts by volume acetone and the solution is poured in water and ice (total amount 200600 parts).

3,416,87 5 3 4 A neutral solution of 0.1 mol (20.9 parts) of in 100130 parts by voumezi cooled at 24 Cflwitgioitfi),

is added dro wise an un er a itation, wi 1n CGHsNHCHZSOaNa minutes, to th e suspension of cyar iuric chloride obtained in 100130 parts water, cooled at 24 C. with ice, is as above described Poured drbpywise and under agitation in the thus During the addition, the temperature of the reaction tained Suspension of the ey'ahtlrie ehioridemass is maintained between 0 and 2 C. and the pH During the addition, the temperature of the reaction between d 6 b i bl pouring d o i f id mass is p between 0 and C": and the P between acceptor solutions (20% Na CO solution; 1 N NaOH 5 and 6 y Suitable Pouring dTOPWiSe 0f the acid acceptor solution; NaHCO solution and if desired, Na acetate). Solutions a a Solution, 1 N NaOH Solution: At the end of the addition of the sodium salt of the NaHCOa Solution and if desired, Na acetate)- anilinomethanesulfonic acid, the agitation is continued At the end 0f th addition of the Sodium Salt of i" until dissolution is completed (about 2 hours), keeping linomethanesulfonic acid, the agitation is continued until h temperature of h reaction mass b t 0 d 2 the dissolution is completed, always keeping the tempera- C and h H between 5 d 6 ture of the reaction mass between 0 and and the After this time the solution obtained is neutralized with pH between 5 and 1 N NaOH or 10% Na CO solution, and if necessary, is

After this period of time, the solution thus obtained p ifi d f traces of i l bl id i neutraliz d With 1 N NaOH 0r NaOH Solution The sodium salt of the monocondensation product, the and if necessary, it is Purified of traces of insoluble resi' 4,6-dichloro-s-triazin-2-y1-anilinomethanesulfonic acid, is due. thus obtained.

The monocondensation product, the sodium salt of 4,6- After 2 hours agitation at 3 c a l i H=7) dichloro-s-triazin-Z-yl-anilinomethanesulfonic acid iS Obof pa -ts mol) of the sodium alt of isogamma tained. After 2 hours agitation at 03 C. a solution of id i 400 parts Water i dd d Parts of the 3'amino'4'sulfoanilihe in The whole is heated at about 40 C. and keeping the 150 Parts Water (P is added- 5 temperature constant the pH is adjusted and maintained T Whole iS heated to about keeping between 5.5 and 6.0 by gradual addition of 50-55 parts this temperature ebhstahithe P is adjusted and p by volume of a 10%w./v. solution of sodium carbonate. between and 64) y gradual addition of 5045 Parts y After 2 hours condensation at about 40 C. the solution volume of a 10% w./v. solution of sodium carbonate. is Cooled at 2 3 and 23 parts 1 mol) f the After 2 b j agitation at a temperature of about diazo of 4-aminoacetanilide-3-sulfonic acid (prepared the Solution 15 cooled to Parts mol) according to BIOS 1548, page 48) is poured therein while of sodium nitrite (in form of an aqueous 20% w/v. soluthe PH is maintained at the value of 7 7'5 by gradual tion), 80 parts of ice and 25.7 parts of 21 Be. HCl in dropwise addition of a 20% solution of Nazcoa form of a i Stream} are.added The dyestuff is then precipitated by salting out, and The reactlon mass 18 agltated for about 10 mmutes at then it is filtered under vacuum and dried in a stove at the temperature of about 3-4 C. 35400 C for 48 hours The suspension of the diazo thus prepared is added within 15 minutes to a solution of 44.6 parts of sodium EXAMPLE 3 salt of the N-benzoyl-H-acid in 200 parts by volume of the 17.5% solution of Na CO cooled at 68 C. and 40 having a pH of about 9. The volume of the solution is 1800 parts by volume. sOiNa ('31 OH The dyestufl? is separated by salting with 15% w./v. T KCl and filtration. It is then dried in a stove at 40 c. w N N HINCOHN I One works exactly as described in Example 2, but the dyestuff having the formula for 48 hours. k EXAMPLE 2 some CH 2 parts of ison1cot1n1c acid and 0.64 part of 100% NaOH are dissolved in 100 parts of water at 70 C. SOBNa 4 parts of the dyestutf is used.

(|)H (I31 CH3C0NHN:N

SOSNE. SOENQ NH-k JA -Q (3H2 SOsNa are added to the solution. 0 A quaternized dyestutf which dyes cotton at 35-40 C., The solution is maintained at the above said temperawith high tinctorial yields, in an orange shade showing ture for a whole night (about 15 hours) and then the very good fastness to washing is obtained. dyestuff, after salting out with NaCl, is separated by The dyestuif to be quaternized used in the process of filtration and dried at C. It may be also separated by this example can be obtained as follows: direct drying. 0.1 mol (18.44 parts) cyanuric chloride is dissolved The dyestuif thus obtained dyes cotton at the temperain 100-150 parts by volume acetone and the solution ture of 35 40 C. with h1gh tinctorial yields, in a scarlet is poured in water and ice (total amount 200-600 parts). shade having excellent wet fastness. Onto the thus obtained suspension of cyanuric chloride,

The dyestutf to be quarternized, used in the process a neutral sol tion of 0.1 mol (20,9 parts) of of the present example, can be obtained as follows:

0.1 mol 18.44 parts) of cyanuric chloride in dissolved C H NHCH SO Na in 100-150 parts by volume of acetone and the solution is poured in water and ice (total amount 200-600 parts). 9 Parts by P i Water cPoled Wlth at A neutral solution of 01 mol (203 pans of 2 trt C. 1s poured within 20-40 minutes and under a gl a lOll.

C H NHCH SO Na During the addition the temperature of the reaction 5 mass is maintained between and 2" C. and the pH between and 6 by suitable pouring of acid acceptor solution (20% Na CO solution; 1 N NaOH solution; NaHCO and if necessary also Na acetate).

At the end of the addition of the sodium salt of anilinomethanesulfonic acid, the agitation is continued until the dissolution is complete about 2 hours), always keeping the temperature of the reaction mass between 0 and 2 C. and the pH between 5 and 6.

After this period of time, the solution obtained is neutralized with 1 N NaOH or with a solution of Na CO and if necessary is made clear from traces of insoluble residue.

Thus the monocondensation product, the sodium salt of 4,6-dichloro-s-triazin-2-yl-anilinornethanesulfonic acid, is obtained.

After two hours agitation at 0-3 C. a solution of 18.8 parts (0.1 mol) of the 3-amino-4-sulfoaniline having a pH 7 in 150 parts water is added. The whole is heated at about 40 C. and the pH is always adjusted at a value between 5.5 and 6.0 by gradual addition of 50-55 parts by volume of a 10% w./v. solution of sodium carbonate.

After 2 hours agitation at about 40 C., the solution is cooled to 2-3 C. and 6.9 parts (0.1 mol) of sodium nitrite (in the form of an aqueous 20% w./v. solution), 80 parts ice and 25.7 parts of 21 B. HCl are added in a thin stream.

The reaction mass is agitated for about 10 minutes at the temperature of 3-4 C.

The suspension of the diazo thus obtained is added within about 30 minutes to a solution of 0.1 mol of carbamylisogarnma acid (in the form of its sodium salt) in 350 parts by volume, together with 150 parts NaCl.

The solution, within 2-3 hours, is added with a 10% solution of Na CO introduced dropwise and keeping the pH at the value of 7-7.5.

The dyestufl is separated by filtration and after washing with a 7% brine is dried in a stove at 40 C. for 48 hours.

EXAMPLE 4 The work is carried out exactly as described in Example 1, but using the dyestuif:

SOaNa The thus obtained quaternized dyestutf dyes cotton from an aqueous bath, at 35-40 C. with very good tinctoria'l yields, in a ruby shade having very good fastness to washing.

The dyestuif to be quaternized used in the process of this example can be obtained as follows:

18.9 parts (0.1 mol) of the 2-aminophenol-4-sulfonic acid are directly diazotized, in suspension, at 0-5" C.

The solution of the diazo (about 250 parts by volume), after neutralization to Congo red with sodium carbonate, is coupled with isogamma acid (25.1 parts corresponding to about 0.105 mol) at pH 9-9.5 and at a temperature of 0-5 C.

The solution of the monoazo thus obtained (volume 500 parts by volume) is heated at 60 C. and is mixed with a 1 equivalent solution of CuSO -5H O (25 parts and with a solution containing 2 equivalents of crystallized sodium acetate (27 parts).

The metallization is complete within 1-2 hours at 60-65 C. and a pH of about 6.

The separation of the Cu complex is carried out after cooling and 10% (w./v.) salting, by filtration.

The cake of the meta'llized monoazo dissolves in 500 parts by volume water, at a pH of 7-7.5. To the solution thus obtained, the solution of 0.13 mol of the monocondensation product between cyanuric chloride and the sodium salt of anilinomethanesulfonic acid, prepared according to the modalities described in Example 1, is added at room temperature.

The solution thus obtained is mixed with 14 parts (0.1 mol) of crystallized sodium acetate, is heated on a water bath at 40-45 C. and is maintained at this temperature for 2-4 hours in order to complete the reaction.

The pH is kept at 5.8-6 by addition of alka-lies (N82C03, Nell-[CO etc.; volume about parts).

EXAMPLE 5 One works as described in Example 1, but using the dyestufi":

S|O Na n ar- A N If I l 1 \N/ on nn- BIT- CH2 -o1 SOaNa o1 S O;Na

The quaternized dyestutf thus obtained dyes cotton from an aqueous bath at 35-40 C.. with very good tinctorial yields in a yellow shade having very good fastness to wet treatments.

The dyestuff to be quaternized used in the process of this example can be obtained as follows:

0.1 mol (18.44 parts) of cyanuric chloride is dissolved in 100-150 parts by volume acetone and the solution is poured on water and ice (200-600 parts in total).

On the suspension of the cyanuric chloride thus obtained, the neutral solution consisting of 0.1 mol (20.9 parts) of C H NHCH SO Na in 100-130 parts by volume water, cooled at 2-4 C. with ice is poured dropwise. During the addition the temperature of the reaction mass is maintained between 0 and 2 C. and the pH between 5 and 6 by suitable pouring dropwise of acid acceptor solutions. (20% solution of Na CO 1 N NaOH, NaHCO and if desired Na acetate).

At the end of the addition of the sodium salt of the anilinomethanesulfonic acid the agitation is continued until the dissolution is complete (about 2 hours), keeping the temperature of the reaction mass between 0 and 2 C. and the pH between 5 and 6.

After this period of time, the solution thus obtained is neutralized with 1 -N NaOH or with 10% solution of Na CO and is purified, if necessary, from the traces of insoluble residue.

Thus, the monocondensation product, the sodium salt of the 4,6-dichloro-s-triazin-2-yl-anilinomethanesulfonic acid is obtained.

After 2 hours agitation at 0-3 C., a solution of 18.8 parts (0.1 mol) of 3-amino-4-sulfoani1ine in parts water having a pH of 7 is added.

The whole is heated at about 40 C. and by keeping this temperature constant, the pH is always adjusted between 5.5 and 6.0 by gradual addition of 50-55 parts by volume of a 10% w./v. solution of sodium carbonate.

After 2 hours agitation at about 40 C. the solution is cooled at 2-3" C. and 6.9 parts (0.1 mol) of sodium nitrite (in form of an aqueous 20% w./v. solution), 80 parts of ice and 25.7 parts of 21 B HCl in form of a thin stream are introduced.

The reaction mass is agitated for about 10 minutes at the temperature of 3-4 C.

The solution of a diazo is poured within 15 minutes in the solution of 32.3 parts (0.1 mol) of 1-(2',5'-

dichloro-4-sulfophenyl)-3-methyl-5-pyrazolone in 150 parts Water and 13 parts sodium carbonate, previously cooled at about 5 C. and added immediately before the coupling with 60 parts of crystallized sodium acetate.

The dyestufr is then precipitated by salting out, filtered under vacuum and dried as much as possible and then dried in a stove at 35-40" C. for 48 hours.

EXAMPLE 6 A dye bath is prepared by dissolving 2 parts by Weight of the dyestulf prepared according to the Example 5, in 2000 parts by volume of water at the temperature of 35 C.

100 parts of the cellulose material are introduced in the dye bath; after minutes 60 parts of anhydrous Na SO are added; after minutes 60 parts of anhydrous Na SO are added; after minutes 15 parts of Na CO are added; after 60 minutes 15 parts of Na CO are added. The bath is maintained at 35 C. for a further hour, in order to complete the fixing of the dyestuff, and then the material is soaped for 30 minutes at boiling with a 3% soap solution.

The material is rinsed thoroughly with water.

A cellulose material dyed in a yellow shade having very good fastness to Wet treatment is obtained, with very good tinctorial yields.

EXAMPLE 7 A dye bath is prepared by dissolving 2 parts by weight of the dyestuif prepared according to the Example 5, in 2000 parts by volume of water, at the temperature of C.

100 parts of the cellulose material are introduced in the dye bath; after 15 minutes at the temperature of 50 C., parts of anhydrous Na SO is added; after 30 minutes at the temperature of 60 C., 60 parts of anhydrous Na SO are added; after 45 minutes at the temperature of C., 15 parts of Na CO are added; after 60 minutes at the temperature of C., 15 parts of Na CO are added. The bath is kept at 80 C. for one further hour. The material is soaped for 30 minutes at the boiling with a soap solution. The material is well rinsed with water.

A cellulose material dyed in a yellow shade having very good fastness to wet treatment is obtained, with very good tinctorial yields.

EXAMPLE 8 2 parts of isonicotinic acid and 0.64 part of NaOH are dissolved in 100 parts of water, at 80 C. 5 parts of the dyestuff:

' SO3Na 1 ONE none sulfonic acid are salified in 1500 parts of water by addition of sodium carbonate.

The mass is then slowly added, at 05 C., to a solution (kept at 05 C.) of the compound obtained according to the description of Example 1 by condensation between 0.1 mol of cyanuric chloride and 0.1 mol of the sodium salt of anilinomethanesulfonic acid added with 10 parts of sodium bicarbonate.

The temperature is then permitted to rise to 20-25 C., and is kept at this value until the condensation is ended.

The dyestuff having the following composition 0 If Hz is separated by salting.

EXAMPLE 9 The operation is carried out exactly as described in Example 8, but using 4 parts of the dyestuff:

N N CH2 C SOaNa wherein Pc means copper phthalocyanine.

The dyestuff obtained dyes cotton at the temperature of 60 C., with good tinctorial yields, in a turquoise shade having very good fastness to washing. The dyestuff to be quaternized used in this process can be obtained as follows:

0.1 mol of the intermediate having the following structure:

wherein Pc means copper phthalocyanine, are added under agitation, in the form of a paste, in 2000 parts of water and the pH is adjusted at a value of 8 by adding little amounts of NaOH.

The solution thus obtained is slowly added at 05 C. to a solution (which is also kept at 05 C.) of the condensation product between 0.1 mol of cyanuric chloride and 0.1 mol of the sodium salt of the anilinomethanesulfonic acid added with 10 parts of sodium bicarbonate.

(The condensation product between cyanuric chloride and the sodium salt of the anilinomethanesulfonic acid can be prepared, for instance, by dissolving, in 500 parts of water, 0.1 mol of the sodium salt of the anilinomethanesulfonic acid and adding 17 parts of sodium bicarbonate and successively, at a temperature of 05 C., a suspension (kept at 05 C.) of 0.1 mol of cyanuric chloride in 1500 parts of water.)

The whole is agitated for some hours at increasing temperature up to 2025 0, till a sample shows that the reaction is ended.

The reaction product is separated by salting.

9 EXAMPLE 10 By working as described in the preceding example, but using the dyestuff having the structure:

a quaternized dyestutf is obtained having characteristics similar to those of the dyestuff of Example 9.

EXAMPLE 11 A dye bath is prepared by dissolving 2 parts by weight of the dyestuff prepared according to the Example 10, in 2000 parts by volume of water at the temperature of 60 C.

100 parts of the cellulose material are introduced in the dye bath; after 15 minutes 60 parts of anhydrous Na SO are added; after 30 minutes 60 parts of anhydrous Na SO are added; after 45 minutes 15 parts of Na CO are added; after 60 minutes 15 parts of Na CO are added.

The bath is maintained at 60 C. for one further hour, in order to complete the fixing of the dyestuff and then the material is soaped for 30 minutes at the boiling point with a 3% soap solution.

A cellulose material dyed in a turquoise shade having very good fastness to wet treatment is obtained with very good tinctorial yields.

With the same procedure, the quaternized dyestuff of Example 8 can also be applied.

What is claimed is:

1. A process for dyeing cellulose textile materials comprising applying thereto a dyestufl? having the formula O SOsNa wherein X is selected from the group consisting of H, CH OCH and OC H n is an integer from 1 to 4; m is 1 or 2 and the chromogen is selected from the group consisting of azo dyestuffs, metallized-azo-dyestuffs, anthraquinone dyestufis, and phthalocyanine dyestuffs.

2. A dyeing process according to claim 1, wherein the dyeing is carried out in the presence of an acid-binding agent at a temperature of from 30 to 90 C.

3. The process of claim 2, wherein an electrolyte is present.

4. A dyeing process according to claim 1, wherein the dyeing is carried out in the presence of an acid-binding agent at a temperature of from 30 to C.

5. The process of claim 4, wherein an electrolyte is present.

6. A dyeing process according to claim 2, wherein the acid-binding agent is selected from the group consisting of an alkaline hydroxide, an alkaline carbonate, an alkaline bicarbonate, and an alkaline triphosphate.

7. A dyeing process according to claim 4, wherein the acid-binding agent is selected from the group consisting of an alkaline hydroxide, an alkaline carbonate, an alkaline bicarbonate, and an alkaline triphosphate.

8. A dyeing process according to claim 3, wherein the electrolyte used is selected from the group consisting of sodium chloride, and sodium sulfate.

9. Cellulose textile materials, in particular fibers, dyed or printed with one or more of the reactive dyestuffs having the formula wherein X is selected from the group consisting of H, CH OCH and OC H n is an integer from 1 to 4; m is 1 or 2 and the chromogen is selected from the group consisting of azo dyestuffs, metallized-azo-dyestuffs, anthraquinone dyestuffs, and phthalocyanine dyestuffs.

References Cited UNITED STATES PATENTS 3,198,595 8/1965 Mawson. 3,206,451 9/1965 Benz et al. 260153 NORMAN G. TORCHIN, Primary Examiner.

T. I. HERBERT, JR., Assistant Examiner.

US. Cl. X.R. 260146, 153 

1. A PROCESS FOR DYEING CELLULOSE TEXTIEL MATERIALS COMPRISING APPLYING THERETO A DYESTUFF HAVING THE FORMULA 